From oximes to tertiary alcohols in water, at room temperature and under air: a hybrid one-pot tandem assembly of enzymatic deoximation and RLi/RMgX reagents

Abstract

The highly efficient biodeoximation of aromatic ketoximes, promoted by the enzymatic oxidative system laccase/TEMPO/O2 has been successfully assembled with the fast and chemoselective addition of highly-polar s-block organometallic reagents (RLi/RMgX)...

Visible‐Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity

“…The authors have cited additional references within the Supporting Information [56–108] . Deposition Number(s) (https://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/anie.202402885) 2313487 (for 2‐amino‐5‐mesityl‐3‐methylpyridine), 2313446 (for 1‐AlPh 2 ), 2313488 (for 2‐AlMe 2 ), 2313489 (for 2‐AlEt 2 ), 2313490 (for 2‐Al i Bu 2 ), 2313491 (for 2‐Al t Bu 2 ), 2313492 (for 2‐AlPh 2 ), 2313493 (for 2‐AlCl 2 ), 2313485 (for 2‐Al(CH=CH 2 ) 2 ), 2313494 (for 2‐Al(C≡C‐TMS) 2 ), 2313495 (for 3‐AlMe 2 ), 2313496 (for 3‐AlPh 2 ) contain(s) the supplementary crystallographic data for this paper.…”

Recent Advancements in the Utilization of s-Block Organometallic Reagents in Organic Synthesis with Sustainable Solvents

“…This innovative one-pot/two-step procedure takes place in aqueous media at room temperature and in the presence of air, yielding the desired tertiary alcohols 41 in moderate to good yields (46-88%). Importantly, this entire process eliminate the need for isolation or purification steps [68]. Moreover, this hybrid approach demonstrated exceptional adaptability, marking its capacity to accommodate less reactive Grignard-type organometallic reagents (RMgX), a novel feat in this domain of chemistry (Scheme 13).…”

“…This review is structured into distinct sections, each highlighting various types of reactivities: (i) chemoselective double addition of RLi/RMgX reagents into esters in DESs or water at room temperature and in the absence of a protective atmosphere [57]; (ii) the potential implementation of RLi/RMgX reagents under continuous, stable and safe reaction conditions in flow at room temperature, assisted by DESs or water [58,59]; (iii) the rapid addition of s-block organometallic reagents to CO 2 -derived cyclic carbonates at room temperature, under air and in 2-MeTHF [60]; (iv) the one-pot/two-step modular double addition of different highly polar organometallic reagents (RLi/RMgX) into nitriles to produce asymmetric tertiary alcohols under aerobic/room temperature and in neat conditions [61]; (v) the fast addition of RLi reagents to amides in environmentally friendly CPME, at ambient temperature and under air [62]; (vi) the highly efficient and selective fast addition of in situ generated lithium amides (obtained via an acid-base reaction between n-BuLi and the desired primary amine) into carbodiimides (R-N=C=N-R) or nitriles (R-C≡N) in 2-MeTHF or CPME [63]; (vii) the Directed ortho-Metalation (DoM) or anionic Fries rearrangement of O-arylcarbamates promoted by lithium amides under aerobic conditions in sustainable reaction media (DESs/CPME) [64]; (viii) the Pd-catalyzed cross-coupling reactions of RLi reagents with o-benzenedisulfonimides [65]; (ix) the electrophilic trapping of in situ generated organosodium intermediates (RNa) in DESs or in pure water, at room temperature and under air [66], and (x) the neopentyl sodium (NpNa)-promoted sodiumhalogen exchange of aromatic products or direct deprotonation of terminal alkynes under mild conditions [66]. Additionally, the final section of this review summarizes ongoing efforts to design hybrid one-pot tandem protocols aimed at synergistically combining aerobic polar s-block organometallic chemistry in green solvents with (i) enzymatic aqueous synthetic protocols, such as oxidations of secondary alcohols into ketones [67] or the biodeoximation of ketoximes [68]; (ii) organic procedures, including the acetylation of diols [69] or tetrahydropyranylation of alcohols, promoted by Brønsted-type acidic DESs [70] and (iii) the Cu-catalyzed oxidation of primary alcohols into the corresponding aldehydes in DESs or water [71].…”

Merging Organolithium Chemistry and Stereoselective Biocatalysis: Transformation of Aromatic Nitriles into Chiral Alcohols

“…[25] In some cases, these hybrid reactions RLi/enzyme have been successfully conducted sequentially in a one-pot manner. Unfortunately, such examples are scarce and mostly involve the combination of laccases with RLi compounds, [26,27] with no reported instances to date of synergistic combination between RLi reagents and enzymes for the development of multi-step stereoselective processes. Consequently, and trying to finish with this discontinuity in the design of stereoselective chemoenzymatic protocols, we decided to focus our interest in exploring the potential combination of organolithium reagents with alcohol dehydrogenases (ADHs), enzymes capable of catalyzing prochiral ketone bioreduction processes, [28][29][30][31] that have previously demonstrated high compatibility with a wide array of chemical reagents and catalysts.…”